CN119252907B - Preparation method and application of hard carbon coated soft carbon composite porous carbon-based anode material - Google Patents
Preparation method and application of hard carbon coated soft carbon composite porous carbon-based anode material Download PDFInfo
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- CN119252907B CN119252907B CN202411773589.9A CN202411773589A CN119252907B CN 119252907 B CN119252907 B CN 119252907B CN 202411773589 A CN202411773589 A CN 202411773589A CN 119252907 B CN119252907 B CN 119252907B
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- 229910021384 soft carbon Inorganic materials 0.000 title claims abstract description 136
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010405 anode material Substances 0.000 title claims description 20
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical group NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229960003638 dopamine Drugs 0.000 claims abstract description 49
- 229920001690 polydopamine Polymers 0.000 claims abstract description 34
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 33
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 33
- 239000011246 composite particle Substances 0.000 claims abstract description 28
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 phenolic aldehyde Chemical class 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 230000003213 activating effect Effects 0.000 claims abstract description 17
- 239000007771 core particle Substances 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 16
- 229910000077 silane Inorganic materials 0.000 claims abstract description 16
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000010000 carbonizing Methods 0.000 claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 238000001994 activation Methods 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229920002866 paraformaldehyde Polymers 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 5
- 239000004005 microsphere Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000007740 vapor deposition Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- 239000011302 mesophase pitch Substances 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000011331 needle coke Substances 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229940074404 sodium succinate Drugs 0.000 claims description 2
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002952 polymeric resin Substances 0.000 claims 1
- 229920003002 synthetic resin Polymers 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052710 silicon Inorganic materials 0.000 abstract description 16
- 239000010703 silicon Substances 0.000 abstract description 16
- 239000007773 negative electrode material Substances 0.000 abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 10
- 229910052744 lithium Inorganic materials 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 36
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 7
- 229920001568 phenolic resin Polymers 0.000 description 7
- 239000005011 phenolic resin Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 229920000151 polyglycol Polymers 0.000 description 5
- 239000010695 polyglycol Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WIEXMPDBTYDSQF-UHFFFAOYSA-N 1,3-bis(furan-2-yl)propan-2-one Chemical compound C=1C=COC=1CC(=O)CC1=CC=CO1 WIEXMPDBTYDSQF-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229920005546 furfural resin Polymers 0.000 description 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 229920000368 omega-hydroxypoly(furan-2,5-diylmethylene) polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
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- 238000011112 process operation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及一种硬碳包覆软碳的复合多孔碳基负极材料的制备方法及应用，包括以下步骤:（S1）将软碳材料前驱体炭化、活化得到软碳内核颗粒；（S2）氧化后的软碳内核颗粒经多巴胺聚乙二醇基硅烷接枝改性后，与多巴胺进行原位共聚反应，得到有机硅‑聚多巴胺包覆软碳的复合颗粒；（S3）在复合颗粒的表面进行酚醛的原位聚合，形成酚醛包覆软碳的复合颗粒；（S4）酚醛包覆软碳的复合颗粒经炭化、活化，得到硬碳包覆软碳的复合多孔碳；（S5）复合多孔碳经硅沉积和碳包覆，得到硬碳包覆软碳的复合多孔碳基负极材料。本发明制得的硬碳包覆软碳的复合多孔碳基负极材料用在锂电池负极时，具有良好的电化学性能，尤其是循环性能和抗压性能优异。
The present invention relates to a preparation method and application of a composite porous carbon-based negative electrode material of hard carbon coated soft carbon, comprising the following steps: (S1) carbonizing and activating a soft carbon material precursor to obtain soft carbon core particles; (S2) the oxidized soft carbon core particles are grafted and modified with dopamine polyethylene glycol silane, and then in-situ copolymerized with dopamine to obtain composite particles of organosilicon-polydopamine coated soft carbon; (S3) in-situ polymerization of phenolic aldehyde is performed on the surface of the composite particles to form composite particles of phenolic aldehyde coated soft carbon; (S4) the composite particles of phenolic aldehyde coated soft carbon are carbonized and activated to obtain composite porous carbon of hard carbon coated soft carbon; (S5) the composite porous carbon is subjected to silicon deposition and carbon coating to obtain composite porous carbon-based negative electrode material of hard carbon coated soft carbon. The composite porous carbon-based negative electrode material of hard carbon coated soft carbon prepared by the present invention has good electrochemical properties, especially excellent cycle performance and compressive resistance when used in the negative electrode of a lithium battery.
Description
Technical Field
The invention belongs to the technical field of secondary battery anode materials, and particularly relates to a preparation method and application of a hard carbon coated soft carbon composite porous carbon-based anode material.
Background
Along with the continuous improvement of the technological development on the energy power demand and the demand of the long-endurance and ultra-fast rechargeable battery, the graphite of the negative electrode material of the traditional lithium battery has been developed to be close to the theoretical capacity. The theoretical specific capacity of the silicon material can reach 4200mAh/g, which is more than 10 times of that of the traditional graphite negative electrode material, however, the main reason that the silicon-based negative electrode material is not applied on a large scale is that the silicon expands 3 times of the original volume in the lithiation process, which is fatal to a lithium battery. The silicon-carbon composite material is an effective means for solving the problem of low specific capacity and relieving the silicon expansion effect at present, such as a chemical vapor deposition silicon-carbon negative electrode material, and is prepared by decomposing silane gas in porous carbon pore canals to generate nano silicon, wherein the performance of a used porous carbon substrate has great influence on a final product. The porous carbon substrate material has hard carbon and soft carbon, and the two materials have advantages and disadvantages. The hard carbon mainly comprises biomass, high molecular organic matters and resins, the biomass hard carbon material is difficult to regulate and control a pore structure through activation due to inherent macropores, the raw materials are greatly influenced by natural environment and are difficult to stabilize, the resin hard carbon material can obtain a porous structure with controllable pore structure through an activation reaction, and the raw materials are stable, low in impurity content and high in structural strength, but high in price and difficult to apply to the power battery market in a large scale. In addition, the short-range disordered structure of the hard carbon leads to higher diffusion rate of lithium ions and good compatibility with electrolyte, so that the lithium ion battery has higher rate capability, but too many holes lead to larger specific surface area and low first charge and discharge efficiency. Soft carbon has wide raw materials, low price, good conductivity and fast lithium ion transmission rate, but cannot effectively bear the volume expansion of silicon due to poor strength and high expansion rate, and is not enough to prevent agglomeration among silicon particles.
The preparation of composite carbon by compositing hard carbon and soft carbon is an important research direction of silicon carbon negative electrode materials by utilizing the respective advantages of the hard carbon and the soft carbon. Chinese patent CN113889593B discloses a preparation method of a hard carbon coated soft carbon composite material, which comprises the following steps of 1) carrying out hydrothermal reaction on precursor liquid containing asphalt compounds, titanium dioxide and an organic solvent to obtain core precursor particles, 2) dissolving a hard carbon precursor, lithium salt and benzenesulfonic acid in the solvent to obtain a coating solution, coating the core precursor particles by using the coating solution, and then carbonizing, wherein the hard carbon precursor is one or more than two of phenolic resin, epoxy resin, polyfurfuryl alcohol, furfural resin, furfuryl ketone resin and furfuryl alcohol resin. The hard carbon coated soft carbon composite material obtained by the method takes TiO 2 doped soft carbon as an inner core, can improve specific capacity and lithium ion transmission capacity, and improves structural stability of the material and safety of battery operation, and the hard carbon in the shell has the characteristics of large interlayer spacing and stable structure, is favorable for improving quick charge performance and cycle performance of the material, and improves primary efficiency and multiplying power performance of the material by supplementing lithium to the hard carbon material through lithium salt.
Chinese patent CN111293301B discloses a soft and hard carbon composite porous negative electrode material for sodium ion battery and its preparation method. The soft and hard carbon composite porous anode material is prepared by regulating and controlling cobalt nitrate, dimethyl imidazole and polyvinyl alcohol. The preparation method comprises the steps of dropwise adding ethanol solution of dimethyl imidazole into ethanol solution of cobalt nitrate, stirring at room temperature to form solution of precursor ZIF-67, adding polyvinyl alcohol into the solution, refluxing to form gel, naturally cooling, freeze-drying, and placing in an inert gas atmosphere at 700-1100 ℃ for 2-5 hours to obtain the anode material. The invention synthesizes a soft carbon source metal organic framework ZIF-67, then adds a hard carbon source PVA to form gel, and obtains a final product after heat treatment. The composite anode material prepared by the invention combines the advantages of excellent conductivity of soft carbon and high capacity of hard carbon, effectively improves the stability of the battery, and improves the cycle performance and coulomb efficiency of the sodium ion battery. The method has the advantages of stable raw material components, simple process operation and high repeatability, and is beneficial to industrial production.
The hard carbon coated soft carbon composite porous carbon prepared in the patent is physically coated, the core-shell has insufficient adhesion, the shell is easy to peel, namely, the structure is not stable enough, and further adverse effects on the cycle performance and the compression resistance can be caused.
Disclosure of Invention
In view of the problem that the composite porous carbon prepared by coating soft carbon with hard carbon has insufficient adhesion between core and shell, namely unstable structure, the invention provides a preparation method of a composite porous carbon-based anode material of soft carbon coated with hard carbon.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the hard carbon coated soft carbon composite porous carbon-based anode material comprises the following steps:
(S1) carbonizing, activating and crushing a soft carbon material precursor to obtain soft carbon core particles;
(S2) soaking soft carbon core particles in an oxidative inorganic strong acid, rinsing and drying after the soaking is finished to obtain oxidized soft carbon, dispersing the oxidized soft carbon in a mixed solution of dopamine polyethylene glycol silane and an aromatic hydrocarbon solvent to carry out a grafting reaction to obtain modified soft carbon, adding the modified soft carbon and dopamine into a Tris-HCl buffer solution to carry out an in-situ copolymerization reaction, and centrifuging, washing and drying after the reaction is finished to obtain the composite particles of organosilicon-polydopamine coated soft carbon, wherein the structural formula of the dopamine polyethylene glycol silane is as follows:
;
wherein R is methyl or ethyl, and n is an integer of 5-15;
(S3) putting the organosilicon-polydopamine coated soft carbon composite particles and a surfactant into an alcohol aqueous solution to form a suspension, then adding a phenolic monomer, paraformaldehyde and an alkali catalyst into the suspension, and heating to perform in-situ polymerization reaction;
(S4) carbonizing and activating the phenolic aldehyde coated soft carbon composite particles to obtain hard carbon coated soft carbon composite porous carbon;
And S5, carrying out chemical vapor deposition on the composite porous carbon by utilizing an organosilicon source gas to enable part or all of nano silicon particles to be attached in the pores of the porous carbon, and then adopting a vapor carbon source to carry out vapor deposition to form a carbon coating layer to obtain the hard carbon coated soft carbon composite porous carbon-based anode material.
After the soft carbon kernel particles are oxidized, rich oxygen-containing functional groups such as-OH, -COOH and the like are generated on the surfaces, so that the subsequent grafting modification is facilitated. When the dopamine polyethylene glycol silane is grafted and modified, oxygen-containing functional groups such as-OH, -COOH and the like on the surface of the soft carbon kernel particles react with the siloxy groups, so that the dopamine polyethylene glycol silane is introduced to the surface of the soft carbon kernel particles through chemical bonds, then the active dopamine groups on the surface of the soft carbon subjected to grafting modification are subjected to copolymerization reaction with dopamine monomers, so that polydopamine is coated on the surface of the soft carbon in situ to form organosilicon-polydopamine coated soft carbon composite particles, and then the organosilicon-polydopamine coated soft carbon composite particles are subjected to in situ polymerization to form phenolic resin, namely a three-layer structure is formed, wherein the inner layer is the soft carbon, the middle layer is the organosilicon-polydopamine, and the outer layer is the phenolic aldehyde. The dopamine polyethylene glycol silane with a certain chain segment length and the short-chain dopamine monomer can form effective complementation, so that the organosilicon-polydopamine of the middle layer compactly, uniformly and stably coats soft carbon, meanwhile, the polydopamine in the middle layer has stronger adhesion performance, and rich benzene-ring diphenol groups and amino groups in the polydopamine can form stronger hydrogen bond acting force with the phenolic aldehyde of the outer layer, so that the binding force between the two is enhanced, the phenolic aldehyde of the outer layer is firmly and stably coated on the middle layer, and in addition, the step (S3) is the in-situ polymerization to form the phenolic aldehyde, so that the stability of the structure is further promoted. Carbonizing and activating the phenolic aldehyde coated soft carbon composite particles to form hard carbon coated soft carbon composite porous carbon which has a three-layer stable structure and is firmly bonded between core shells, wherein the inner layer of the three-layer structure is soft carbon, the middle layer is organic silicon-carbon, and the outer layer is hard carbon; finally, chemical vapor silicon deposition and carbon coating are carried out to form the hard carbon coated soft carbon composite porous carbon-based anode material.
The polymerization degree of polyethylene glycol chain segments in the dopamine polyethylene glycol silane is required to be in the above range, and if the polymerization degree is too high, the active phenolic hydroxyl groups in the formed organosilicon-polydopamine are relatively less, so that the bonding force between the organosilicon-polydopamine and the outer phenolic resin is weak, the structural stability of the composite porous carbon is poor, and the structure of part of pores is collapsed during activation. The degree of polymerization is less, and the chain segment is too short, and can not be effectively complemented with the dopamine monomer to form a compact intermediate layer, so that the structural stability of the composite porous carbon is poor, and the structure of part of the pores is collapsed during activation.
Further, in the step (S1), the soft carbon material precursor is at least one of needle coke, petroleum coke, carbon fiber, and mesophase pitch microsphere.
Further, in the step (S1), the carbonization condition is that the temperature is kept at 300-800 ℃ for 3-8 hours under an inert atmosphere, the inert atmosphere is nitrogen and/or argon, the activation condition is that at least one of KOH, naOH, KHCO 3、NaHCO3 is used as an activating agent, the mass ratio of the carbonized soft carbon material precursor to the activating agent is 1:2-5, the temperature is 700-900 ℃, and the time is 2-6 hours.
Further, in the step (S1), the particle diameter D50 of the soft carbon core particles is 3-10 mu m, the specific surface area is 1500-2500 m 2/g, and the pore volume is 0.5-1.5 cm 3/g.
Further, in the step (S2), the dosage ratio of the soft carbon core particles to the oxidizing inorganic strong acid is 100g (500-1000) mL, the oxidizing inorganic strong acid is 3-5 mol/L nitric acid and/or sulfuric acid, the soaking condition is that the temperature is 40-60 ℃ for 2-6 hours, the rinsing is water washing to be neutral, and the drying is that the moisture is less than 5wt%.
In the step (S2), the dosage ratio of the oxidized soft carbon to the dopamine polyethylene glycol silane to the aromatic hydrocarbon solvent is 100g (60-90) mL (500-1000) mL, the aromatic hydrocarbon solvent is at least one of toluene and xylene, and the grafting reaction condition is that the grafting reaction is carried out under the condition of heating to 100-120 ℃ and carrying out reflux reaction for 20-30 hours.
Further, in the step (S2), the dosage of the dopamine is 8-15wt% of that of the modified soft carbon, the dosage ratio of the dopamine to the Tris-HCl buffer solution is (5-10) g, the concentration of the Tris-HCl buffer solution is 10-25 mM, the pH is 8.0-9.0, the condition of in-situ copolymerization reaction is that stirring reaction is carried out for 4-8 hours at 20-30 ℃, and the condition of drying is that drying is carried out for 12-24 hours at 60-80 ℃ in a vacuum oven.
Further, in the step (S3), the mass ratio of the organosilicon-polydopamine coated soft carbon composite particles to the phenolic monomer is 100 (25-40), preferably 100 (30-35).
Further, in the step (S3), the amount of the surfactant is 2-4wt% of the composite particles of the organic silicon-polydopamine coated soft carbon, the molar ratio of the phenolic monomer to the paraformaldehyde is 1 (1.5-1.6), the molar amount of the paraformaldehyde is calculated by the monomer formaldehyde, and the amount of the base catalyst is 2-3wt% of the phenolic monomer.
Further, in the step (S3), the surfactant is at least one of sodium succinate sulfonate, sodium dodecyl sulfonate and sodium fatty alcohol polyoxyethylene ether sulfate, the concentration of alcohol in the alcohol-water solution is 15-30wt%, the alcohol is ethanol, propanol or isopropanol, the phenolic monomer is at least one of phenol, cresol and xylenol, and the alkali catalyst is ammonia water or inorganic alkali, for example, the inorganic alkali is KOH or NaOH.
Further, in the step (S3), the in-situ polymerization reaction is carried out at a temperature of 70-90 ℃ for 3-6 hours, and the drying and curing are carried out at a temperature of 80-100 ℃ for 24-48 hours.
Further, in the step (S4), the carbonization condition is that the temperature is kept at 300-800 ℃ for 3-8 hours under an inert atmosphere, the inert atmosphere is nitrogen and/or argon, the activation condition is that at least one of steam, carbon dioxide, ammonia and hydrogen sulfide is used as an activating agent, the temperature is 800-1000 ℃ for 4-8 hours, and the dosage ratio of the carbonized phenolic aldehyde coated soft carbon composite particles to the activating agent is 1g (10-20) L.
Further, in the step (S4), the particle diameter D50 of the composite porous carbon of the hard carbon coated soft carbon is 5-15 mu m, the specific surface area is 1800-3000 m 2/g, and the pore volume is 0.7-1.2 cm 3/g.
In step (S5), the process of vapor depositing silicon and carbon coatings is well known to those skilled in the art. If the organic silicon source gas is adopted for carrying out vapor deposition on silicon, the dosage ratio of the composite porous carbon to the organic silicon source gas is 1kg (150-300L), the organic silicon source gas is at least one of silane, disilane, trichlorosilane, silicon tetrachloride and silicon tetrafluoride, if the gas phase carbon source is adopted for carrying out carbon coating, the dosage ratio of the composite porous carbon to the gas phase carbon source is 1kg (250-500L), and the gas phase carbon source is at least one of C1-4 alkane, C2-4 alkene and C2-4 alkyne.
In a second aspect, the present invention provides a hard carbon coated soft carbon composite porous carbon-based anode material prepared by the aforementioned preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1) The method comprises the steps of carrying out surface grafting modification on a porous soft carbon inner core by adopting dopamine polyethylene glycol silane to form modified porous carbon, carrying out in-situ copolymerization on the modified porous carbon inner core and a dopamine monomer to form organosilicon-polydopamine coated soft carbon composite particles, and carrying out in-situ polymerization on the surfaces of the organosilicon-polydopamine coated soft carbon composite particles to form phenolic resin, wherein a three-layer structure is formed, the inner layer is soft carbon, the middle layer is organosilicon-polydopamine, and the outer layer is phenolic. The dopamine polyethylene glycol silane with a certain chain segment length and the short-chain dopamine monomer can form effective complementation, so that the organosilicon-polydopamine of the middle layer compactly, uniformly and stably coats soft carbon, meanwhile, the polydopamine in the middle layer has stronger adhesion performance, and rich benzene-ring diphenol groups and amino groups in the polydopamine can form stronger hydrogen bond acting force with phenolic resin, so that the binding force between the two is enhanced, the phenolic resin of the outer layer is firmly and stably coated on the middle layer, and in addition, the step (S3) is to form phenolic aldehyde through in-situ polymerization, so that the structural stability is further promoted. Carbonizing and activating the phenolic aldehyde coated soft carbon composite particles to form hard carbon coated soft carbon composite porous carbon which has a three-layer stable structure and is firmly bonded between core shells, wherein the inner layer of the three-layer structure is soft carbon, the middle layer is organic silicon-carbon, and the outer layer is hard carbon; finally, chemical vapor silicon deposition and carbon coating are carried out to form the hard carbon coated soft carbon composite porous carbon-based anode material.
2) The organic silicon-polydopamine in the middle layer of the composite porous carbon prepared by the invention contains silicon and nitrogen elements, realizes that a layer of organic silicon reticular film is formed in the structure, has high bond energy of Si-O bonds and good stability, simultaneously realizes nitrogen atom doping of the anode material, is beneficial to improving the electrochemical performance and prolonging the cycle life.
3) When the hard carbon coated soft carbon composite porous carbon-based negative electrode material prepared by the invention is used as a silicon carbon negative electrode of a lithium battery, the material has good cycle stability and excellent compression resistance.
Drawings
FIG. 1 is a TEM image of a hard carbon coated soft carbon composite porous carbon obtained in the step (S4) of example 1;
fig. 2 is a first charge-discharge curve of a lithium battery assembled from the hard carbon-coated soft carbon composite porous carbon-based negative electrode material prepared in example 1 at a 0.1C rate.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
The experimental methods described in the examples below, unless otherwise indicated, are conventional, and the reagents and materials, unless otherwise indicated, are commercially available.
The dopamine polyethylene glycol triethoxysilane is selected from the group consisting of new technology limited company of Siamikade, wherein,
The number average molecular weight of the dopamine polyethylene glycol triethoxysilane X1 and the polyglycol chain segments is 500, namely the average polymerization degree n is about 11;
The number average molecular weight of the dopamine polyethylene glycol triethoxysilane X2 and the polyglycol chain segment is 200, namely the average polymerization degree n is about 5;
the number average molecular weight of the dopamine polyethylene glycol triethoxysilane X3 and the polyglycol chain segments is 650, namely the average polymerization degree n is about 15;
the number average molecular weight of the dopamine polyethylene glycol triethoxysilane X4 and the polyglycol chain segment is 1000, namely the average polymerization degree n is about 23;
the number average molecular weight of the dopamine polyethylene glycol triethoxysilane X5 and the polyglycol chain segment is 100, namely the average polymerization degree n is about 2.
Example 1
(S1) carbonizing mesophase pitch microspheres for 4 hours at 700 ℃ in a nitrogen atmosphere to obtain mesophase carbon microspheres, then mixing the mesophase carbon microspheres with KOH according to a mass ratio of 1:2.5, activating for 3 hours at 800 ℃ in the nitrogen atmosphere, adding the obtained material into a hydrochloric acid solution with the concentration of 1M at 40 ℃ after the activation is finished, stirring and washing to be neutral, washing with water, drying at 90 ℃ for 12 hours, and crushing to obtain soft carbon core particles with the D50 of 6.2 mu M;
(S2) placing 300g of soft carbon core particles in 2000 mL mol/L nitric acid, soaking for 3 hours at 50 ℃, rinsing to neutrality by pure water after soaking, drying for 12 hours at 90 ℃ to obtain oxidized soft carbon, dispersing 200g of oxidized soft carbon in 120mL of mixed solution of dopamine polyethylene glycol triethoxysilane X1 and 1500mL of toluene, carrying out reflux reaction for 24 hours at 100 ℃ under stirring, centrifuging after the reaction is finished, drying for 24 hours at 80 ℃ to obtain modified soft pore carbon, adding 100g of modified soft carbon and 8g of dopamine into 1000mL of Tris-HCl buffer solution (with the concentration of 20mM and the pH of 8.5), carrying out stirring reaction for 5 hours at 25 ℃, centrifuging, washing after the reaction is finished, and drying for 24 hours at 80 ℃ to obtain the composite particles of the organosilicon-polydopamine coated soft carbon;
(S3) adding 100g of organosilicon-polydopamine coated soft carbon composite particles and 3g of sodium dodecyl sulfate into an ethanol water mixed solution with the concentration of 20wt% of alcohol to form a suspension, then adding 25g of phenol, 12g of paraformaldehyde and 0.5g of NaOH into the suspension, heating to 80 ℃ for stirring reaction for 5 hours, centrifuging after the reaction is finished, and drying and curing at 80 ℃ for 24 hours to obtain phenolic aldehyde coated soft carbon composite particles;
(S4) taking 50g of phenolic aldehyde coated soft carbon composite particles, carbonizing for 5 hours under the atmosphere of 700 ℃ and nitrogen, continuously heating to 950 ℃, switching nitrogen into carbon dioxide, activating for 6 hours at the flow of 1.5L/min, switching carbon dioxide into nitrogen after the activation, stopping heating and naturally cooling to room temperature, and obtaining hard carbon coated soft carbon composite porous carbon;
(S5) placing 30g of hard carbon coated soft carbon composite porous carbon in a CVD furnace, introducing helium at the rotating speed of the CVD furnace of 20rpm and at the flow rate of 5L/min, heating to 600 ℃ in a helium environment, then maintaining the flow rate of helium, introducing monosilane gas at the flow rate of 0.1L/min, performing chemical vapor deposition for 1h to enable part or all of formed silicon particles to be attached in the pores of the porous carbon, stopping introducing monosilane gas after the silane deposition, continuously introducing helium at the flow rate of 5L/min to remove redundant monosilane gas, introducing acetylene gas at the flow rate of 0.2L/min, performing vapor deposition for 1h at the temperature of 600 ℃, and depositing carbon particles formed after the decomposition of the acetylene gas on the surfaces of a plurality of carbon blocks to form a carbon coating layer, thereby finally obtaining the hard carbon coated soft carbon composite porous carbon-based anode material.
The specific surface area of the core particles obtained in the step (S1) was 1815 m 2/g as measured by the BET method, and the average pore volume was 0.852cm 3/g. The D50 of the hard carbon coated soft carbon composite porous carbon obtained in the step (S4) was 8.9 μm as measured by a particle size analyzer.
A TEM image of the hard carbon coated soft carbon composite porous carbon obtained in step (S4) is shown in fig. 1.
Example 2
The remainder was the same as in example 1 except that in step (S2), the amount of dopamine polyethylene glycol triethoxysilane was 150 mL and the amount of dopamine was 12g.
Example 3
The remainder was the same as in example 1 except that in step (S2), the amount of dopamine polyethylene glycol triethoxysilane was 180 mL and the amount of dopamine was 15g.
Example 4
The remainder is the same as in example 1, except that in step (S2), dopamine polyethylene glycol triethoxysilane X2 is used instead of dopamine polyethylene glycol triethoxysilane X1.
Example 5
The remainder is the same as in example 1, except that in step (S2), dopamine polyethylene glycol triethoxysilane X3 is used instead of dopamine polyethylene glycol triethoxysilane X1.
Example 6
The remainder was the same as in example 1 except that in step (S3), the amount of phenol was 30g, the amount of paraformaldehyde was 15g, and the amount of NaOH was 0.6 g.
Example 7
The remainder was the same as in example 1 except that in step (S3), the amount of phenol was 35g, the amount of paraformaldehyde was 17g, and the amount of NaOH was 0.7g.
Example 8
The remainder was the same as in example 1 except that in step (S3), the amount of phenol was 40g, the amount of paraformaldehyde was 20g, and the amount of NaOH was 0.8g.
Comparative example 1
The rest is the same as in example 1, except that step (S2) is omitted, and the soft carbon core particles prepared in step (S1) are used in step (S3) to replace the porous carbon of the organosilicon-polydopamine coated soft carbon.
Comparative example 2
The remainder is the same as in example 1, except that in step (S2), dopamine polyethylene glycol triethoxysilane X4 is used instead of dopamine polyethylene glycol triethoxysilane X1.
Comparative example 3
The rest is the same as in example 1, except that in step (S2), dopamine polyethylene glycol triethoxysilane X5 is used instead of dopamine polyethylene glycol triethoxysilane X1.
Application example 1
The hard carbon coated soft carbon composite porous carbon-based negative electrode material prepared in example 1 was applied to a negative electrode of a lithium ion battery, assembled into a lithium battery, and tested for electrochemical properties. The preparation method comprises the steps of mixing a hard carbon coated soft carbon composite porous carbon-based negative electrode material, super P, a carbon nano tube, a carboxymethyl cellulose and a styrene-butadiene rubber composite binder according to a mass ratio of 80:9.8:0.2:10 to prepare slurry (CMC and SBR mass ratio is 1:1), coating the slurry on copper foil by using a200 mu m thick scraper, drying in the air, placing the copper foil in a vacuum drying room to prepare a silicon-based negative electrode plate after drying in vacuum of 12h, then taking metallic lithium as a counter electrode and polyolefin as a diaphragm, taking 1 mol/L LiPF6 (a mixed solution of ethylene carbonate and dimethyl carbonate with a volume ratio of 1:1) as an electrolyte, adding 2% of VC and 5% of FEC into the electrolyte, and assembling the composite porous carbon-based negative electrode plate in a German Braun inert gas glove box in an argon atmosphere. And (3) carrying out charge and discharge tests on the assembled battery on a LAND charge and discharge tester, wherein the charge and discharge interval is 50 mV-1.5V, the compaction density is 1.1 g/cm 3, and after three times of charge and discharge under the current density of 0.1C (1C =1500 mA/g), the multiplying power charge and discharge tests are respectively carried out under the current densities of 1C and 5C.
Application examples 2 to 8
Other conditions were the same as in application example 1, except that the hard carbon-coated soft carbon composite porous carbon-based anode materials were prepared in examples 2 to 8, respectively.
Comparative application examples 1 to 3
Other conditions were the same as in application example 1, except that the hard carbon-coated soft carbon composite porous carbon-based anode materials were prepared in comparative examples 1 to 3, respectively.
Testing and analysis
1) The hard carbon coated soft carbon composite porous carbon was subjected to the following performance test, and the data are shown in table 1.
Determination of specific surface area and pore size distribution according to GB/T19587-2017 gas adsorption BET method, TRISTAR II 3020 type full-automatic specific surface area and pore size analyzer manufactured by U.S. Micromeritics Instrument Corporation is adopted to perform low-temperature nitrogen adsorption experiment on the hard carbon coated soft carbon composite porous carbon prepared in examples and comparative examples, and pore size distribution and specific surface area of the composite porous carbon are determined.
TABLE 1 Performance test of hard carbon coated Soft carbon composite porous carbon
。
As can be seen from Table 1, the hard carbon coated soft carbon composite porous carbon prepared by the preparation embodiment of the invention has higher specific surface area than that of soft carbon inner core particles, and meanwhile, the middle layer organosilicon-polydopamine contains silicon and nitrogen elements, so that a layer of organosilicon reticular membrane and nitrogen atom doping are formed in the structure, and the electrochemical performance is improved.
The specific surface area of the hard carbon coated soft carbon composite porous carbon prepared in comparative example 1 is lower than that of the examples, probably because the phenolic coated soft carbon composite particles formed after omitting step (S2) do not contain an organosilicon-polydopamine intermediate layer, the bonding force between the carbonized soft carbon inner core layer and the hard carbon outer layer is weak, the structure of part of the pores is collapsed in the subsequent activation pore-forming process, and the composite porous carbon prepared in comparative example 1 does not contain nitrogen elements because of the absence of the organosilicon-polydopamine intermediate layer.
The specific surface area of the hard carbon coated soft carbon composite porous carbon prepared in comparative example 2 is lower than that of the embodiment, probably because the polymerization degree of the dopamine polyethylene glycol triethoxysilane is larger, the active phenolic hydroxyl in the formed organosilicon-polydopamine is relatively less, so that the bonding force between the organosilicon-polydopamine and the outer phenolic resin is weaker, the structural stability of the composite porous carbon is poorer, and the structure of part of pores is collapsed during activation.
The specific surface area of the hard carbon coated soft carbon composite porous carbon prepared in comparative example 3 is lower than that of the embodiment, probably because the polymerization degree of the dopamine polyethylene glycol triethoxysilane is smaller, the chain segment is too short, the chain segment and the dopamine monomer cannot be effectively complemented to form a compact middle layer, the structural stability of the composite porous carbon is poor, and the structure of part of the pores is collapsed during activation.
As can be seen from comparison of the surface areas of the soft carbon core particles, the specific surface areas of the composite porous carbon prepared in comparative examples 1,2 and 3 are reduced, and the composite porous carbon is unstable in structure and is caused by collapse of the pore structure in the subsequent carbonization and activation processes.
2) Electrochemical performance test the batteries assembled in the application examples and the comparative application examples are subjected to charge and discharge tests on a LAND charge and discharge tester, wherein the electric interval is 50 mV-1.5V, the compaction density is 1.1 g/cm < 3 >, and the batteries are subjected to three charge and discharge tests under the condition that the current density is 0.1C (1C =1500 mA/g). The battery performance test data are shown in table 2.
Table 2 electrochemical performance test
。
As can be seen from the data in table 2, when the hard carbon coated soft carbon composite porous carbon-based negative electrode material prepared by the preparation method is used as a negative electrode of a lithium battery, the first reversible capacity of the material reaches 1850mAh/g, the first coulomb efficiency reaches 88% or more, and the retention rate of discharge capacity of the material after 100 times of circulation can reach 89% or more, which indicates that the assembled lithium battery has good circulation stability and charge-discharge capacity. The first-effect attenuation rate of the hard carbon coated soft carbon composite porous carbon-based anode material prepared by the method is lower than 5% under the pressure of 10t, which indicates that the material has good structural stability.
The foregoing detailed description is directed to one of the possible embodiments of the present invention, which is not intended to limit the scope of the invention, but is to be accorded the full scope of all such equivalents and modifications so as not to depart from the scope of the invention.
Claims (10)
1. The preparation method of the hard carbon coated soft carbon composite porous carbon-based anode material is characterized by comprising the following steps of:
(S1) carbonizing, activating and crushing a soft carbon material precursor to obtain soft carbon core particles;
(S2) soaking soft carbon core particles in an oxidative inorganic strong acid, rinsing and drying after the soaking is finished to obtain oxidized soft carbon, dispersing the oxidized soft carbon in a mixed solution of dopamine polyethylene glycol silane and an aromatic hydrocarbon solvent to carry out a grafting reaction to obtain modified soft carbon, adding the modified soft carbon and dopamine into a Tris-HCl buffer solution to carry out an in-situ copolymerization reaction, and centrifuging, washing and drying after the reaction is finished to obtain the composite particles of organosilicon-polydopamine coated soft carbon, wherein the structural formula of the dopamine polyethylene glycol silane is as follows:
;
wherein R is methyl or ethyl, and n is an integer of 5-15;
(S3) putting the organosilicon-polydopamine coated soft carbon composite particles and a surfactant into an alcohol aqueous solution to form a suspension, then adding a phenolic monomer, paraformaldehyde and an alkali catalyst into the suspension, and heating to perform in-situ polymerization reaction;
(S4) carbonizing and activating the phenolic aldehyde coated soft carbon composite particles to obtain hard carbon coated soft carbon composite porous carbon;
And S5, carrying out chemical vapor deposition on the composite porous carbon by utilizing an organosilicon source gas to enable part or all of nano silicon particles to be attached in the pores of the porous carbon, and then adopting a vapor carbon source to carry out vapor deposition to form a carbon coating layer to obtain the hard carbon coated soft carbon composite porous carbon-based anode material.
2. The method according to claim 1, wherein in the step (S1), the soft carbon material precursor is at least one of needle coke, petroleum coke, carbon fiber, mesophase pitch microsphere, and/or
The carbonization condition is that the temperature is kept at 300-800 ℃ for 3-8 hours under an inert atmosphere, the inert atmosphere is nitrogen and/or argon, the activation condition is that at least one of KOH, naOH, KHCO 3、NaHCO3 is taken as an activating agent, the mass ratio of a carbonized soft carbon material precursor to the activating agent is 1:2-5, the temperature is 700-900 ℃ and the time is 2-6 hours, and/or
The particle diameter D50 of the soft carbon core particles is 3-10 mu m, and the specific surface area is 1500-2500 m 2/g.
3. The preparation method of the soft carbon core particles, according to claim 1, is characterized in that in the step (S2), the dosage ratio of the soft carbon core particles to the oxidative inorganic strong acid is 100g (500-1000) mL, the oxidative inorganic strong acid is 3-5 mol/L nitric acid and/or sulfuric acid, the soaking condition is that the temperature is 40-60 ℃ for 2-6 h, the rinsing is water washing to be neutral, and the drying is that the moisture is <5wt%.
4. The preparation method of the polymer resin composite material is characterized in that in the step (S2), the dosage ratio of the oxidized soft carbon, the dopamine polyethylene glycol silane and the aromatic hydrocarbon solvent is 100g (60-90) mL (500-1000) mL, the aromatic hydrocarbon solvent is at least one of toluene and xylene, and the grafting reaction condition is that the mixture is heated to 100-120 ℃ and the reflux reaction is carried out for 20-30 hours.
5. The preparation method of the modified soft carbon material is characterized in that in the step (S2), the consumption of the dopamine is 8-15 wt% of modified soft carbon, the consumption ratio of the dopamine to Tris-HCl buffer solution is (5-10) g/1000 mL, the concentration of the Tris-HCl buffer solution is 10-25 mM, the pH is 8.0-9.0, the condition of in-situ copolymerization reaction is that stirring reaction is carried out for 4-8 h at 20-30 ℃, and the condition of drying is that drying is carried out for 12-24 h at 60-80 ℃ in a vacuum oven.
6. The preparation method of claim 1, wherein in the step (S3), the mass ratio of the organosilicon-polydopamine coated soft carbon composite particles to the phenolic monomer is 100 (25-40).
7. The preparation method of claim 6, wherein in the step (S3), the mass ratio of the organosilicon-polydopamine coated soft carbon composite particles to the phenolic monomer is 100 (30-35).
8. The method according to claim 1, wherein in the step (S3), the surfactant is used in an amount of 2 to 4wt% based on the composite particles of the silicone-polydopamine coated soft carbon, the molar ratio of the phenolic monomer to paraformaldehyde is 1 (1.5 to 1.6), the molar amount of paraformaldehyde is calculated as monomer formaldehyde, the base catalyst is used in an amount of 2 to 3wt% based on the phenolic monomer, and/or
The surfactant is at least one of sodium succinate sulfonate, sodium dodecyl sulfonate and sodium fatty alcohol polyoxyethylene ether sulfate, the concentration of alcohol in the alcohol water solution is 15-30wt%, the alcohol is ethanol, propanol or isopropanol, the phenolic monomer is at least one of phenol, cresol and xylenol, the base catalyst is ammonia water or inorganic base, and/or
The in-situ polymerization reaction is carried out at a temperature of 70-90 ℃ for 3-6 hours, and the drying and curing conditions are carried out at a temperature of 80-100 ℃ for 24-48 hours.
9. The preparation method of the phenolic aldehyde coated soft carbon is characterized in that in the step (S4), the carbonization condition is that the temperature is kept at 300-800 ℃ for 3-8 hours under an inert atmosphere, the inert atmosphere is nitrogen and/or argon, the activation condition is that at least one of steam, carbon dioxide, ammonia and hydrogen sulfide is used as an activating agent, the temperature is 800-1000 ℃ for 4-8 hours, and the dosage ratio of the carbonized phenolic aldehyde coated soft carbon composite particles to the activating agent is 1g (10-20) L.
10. The method according to claim 1, wherein in the step (S4), the hard carbon-coated soft carbon composite porous carbon has a particle diameter D50 of 5 to 15 μm, a specific surface area of 1800 to 3000m 2/g, and a pore volume of 0.7 to 1.2cm 3/g.
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